Method for the preparation of cathode active material and method for the preparation of non-aqueous electrolyte

ABSTRACT

A LiFePO 4  carbon composite material is to be synthesized in a single phase satisfactorily to achieve superior cell characteristics. In preparing a cathode active material, a starting material for synthesis of a compound represented by the general formula Li x FePO 4 , where  0&lt; x≦ 1,  is mixed, milled and sintered and a carbon material is added to the resulting mass at an optional time point in the course of mixing, milling and sintering. Li 3 PO 4 , Fe 3 (PO 4 ) 2  or its hydrates Fe 3 (PO 4 ) 2   .n H 2 O, where n denotes the number of hydrates, are used as the starting material for synthesis of Li x FePO 4 . The particle size distribution of particles of the starting material for synthesis following the milling with the particle size not less than  3 μ m is set to  2.2 % or less in terms of the volumetric integration frequency.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] This invention relates to a method for the preparation of a cathode active material, capable of reversibly doping/undoping lithium, and to a method for the preparation of a non-aqueous electrolyte cell employing ths cathode active material.

[0003] 2. Description of Related Art

[0004] Nowadays, in keeping up with the recent marked progress in the electronic equipment, researches into re-chargeable secondary cells, as power sources usable conveniently and economically for prolonged time, are underway. Representative of the secondary cells are lead accumulators, alkali accumulators and non-aqueous electrolyte secondary cells.

[0005] Of the above secondary cells, lithium ion secondary cells, as non-aqueous electrolyte secondary cells, have such merits as high output and high energy density. The lithium ion secondary cells are made up of a cathode and an anode, including active materials capable of reversibly doping/undoping lithium ions, and a non-aqueous electrolyte.

[0006] As the anode active material, metal lithium, lithium alloys, such as Li—Al alloys, electrically conductive high molecular materials, such as polyacetylene or polypyrrole, doped with lithium, inter-layer compounds, having lithium ions captured into crystal lattices, or carbon materials, are routinely used. As the electrolytic solutions, the solutions obtained on dissolving lithium salts in non-protonic organic solvents, are used.

[0007] As the cathode active materials, metal oxides or sulfides, or polymers, such as TiS₂, MoS₂, NbSe₂ or V₂O₅, are used. The discharging reaction of the non-aqueous electrolyte secondary cells, employing these materials, proceeds as lithium ions are eluated into the electrolytic solution in the anode, whilst lithium ions are intercalated into the space between the layers of the cathode active material. In charging, a reaction which is the reverse of the above-described reaction proceeds, such that lithium is intercalated in the cathode. That is, the process of charging/discharging occurs repeatedly by the repetition of the reaction in which lithium ions from the anode make an entrance into and exit from the cathode active material.

[0008] As the cathode active materials for the lithium ion secondary cells, LiCoO₂, LiNiO₂ and LiMn₂O₄, for example, having a high energy density and a high voltage, are currently used. However, these cathode active materials containing metallic elements having low Clarke number in the composition thereof, are expensive, while suffering from supply difficulties. Moreover, these cathode active materials are relatively high in toxicity and detrimental to environment. For this reason, novel cathode active materials, usable in place of these materials, are searched.

[0009] On the other hand, it is proposed to use LiFePO₄, having an olivinic structure, as a cathode active material for the lithium ion secondary cells. LiFePO₄ has a high volumetric density of 3.6 g/cm³ and is able to develop a high potential of 3.4 V, with the theoretical capacity being as high as 170 mAh/g. In addition, LiFePO₄ in an initial state has an electro-chemically undopable Li at a rate of one Li atom per each Fe atom, and hence is a promising material as a cathode active material for the lithium ion secondary cell. Moreover, since LiFePO₄ includes iron, as an inexpensive material rich in supply as natural resources, it is lower in cost than LiCoO₂, LiNiO₂ or LiMn₂O₄, mentioned above, while being more amenable to environment because of lower toxicity.

[0010] However, LiFePO₄ is low in electronic conduction rate, such that, if this material is used as a cathode active material, the internal resistance in the cell tends to be increased. The result is that the polarization potential on cell circuit closure is increased due to increased internal resistance of the cell to decrease the cell capacity. Moreover, since the true density of LiFePO₄ is lower than that of the conventional cathode material, the charging ratio of the active material cannot be increased sufficiently if LiFePO₄ is used as the cathode active material, such that the energy density of the cell cannot be increased sufficiently.

[0011] So, a proposal has been made to use a composite material of a carbon material and a compound of an olivinic structure having the general formula of Li_(x)FePO₄ where 0<x≦1, referred to below as LiFePO₄ carbon composite material, as a cathode active material.

[0012] As a method for the preparation of an LiFePO₄ carbon composite material having such olivinic structure, there is proposed such a method consisting in mixing lithium phosphate Li₃PO₄, Fe₃(PO₄)₂ or its hydrates Fe₃(PO₄)₂ .nH₂O, where n denotes the number of hydrates, as starting material for synthesis, adding carbon to the resulting mixture and sintering the resulting product at a preset temperature.

[0013] For producing the LiFePO₄ carbon composite material, the sintering temperature for the mixture needs to be higher than the temperature for which surface activity of the starting materials for synthesis can be exhibited. Since the melting point of Li₃PO₄, Fe₃(PO₄)₂ or its hydrates Fe₃(PO₄)₂ .nH₂O, where n denotes the number of hydrates, as starting material for synthesis of Li_(x)FePO₄, is 800° C. or higher, sufficient surface activity of the starting materials for synthesis can be manifested by setting the sintering temperature to 800° C. or higher. However, if the sintering temperature is high, the energy consumption required for synthesis is increased, as a result of which the production cost is raised. Moreover, a higher sintering temperature means an increased load on e.g., a unit for synthetic reaction, and hence is not desirable for mass production.

[0014] Therefore, the sintering temperature of approximately 600° C. in synthesizing the LiFePO₄ carbon composite material is most desirable for the performance of the cathode active material. However, the particle size of the starting materials for synthesis of the LiFePO₄ carbon composite material is usually 2 to 10 μm. If the sintering temperature is 600° C., sufficient surface activity cannot be developed in sintering on the surface of the starting material for synthesis having this particle size. The result is that difficulties are encountered in achieving single-phase synthesis of the LiFePO₄ carbon composite material.

SUMMARY OF THE INVENTION

[0015] In view of the above depicted status of the art, it is an object of the present invention to provide a method for the preparation of a cathode active material by means of which the reaction efficiency in sintering can be improved such that single-phase synthesis of the LiFePO₄ carbon composite material can be attained even at a sintering temperature of 600° C. lower than the melting point of the starting materials for synthesis thereby realizing superior cell characteristics.

[0016] It is another object of the present invention to provide a method for the preparation of the non-aqueous electrolyte cell having superior cell characteristics such as cell capacity or cyclic characteristics through the use of the so-produced LiFePO₄ carbon composite material as the cathode active material.

[0017] In one aspect, the present invention provides a method for the preparation of a cathode active material comprising:

[0018] mixing, milling and sintering a starting material for synthesis of a compound represented by the general formula Li_(x)FePO₄, where 0<x≦1, and adding a carbon material to the resulting mass at an optional time point in the course of said mixing, milling and sintering;

[0019] employing Li₃PO₄, Fe₃(PO₄)₂ or hydrates Fe₃(PO₄)₂ .nH₂O thereof, where n denotes the number of hydrates, as the material for synthesis of said Li_(x)FePO₄; and

[0020] setting the particle size distribution of particles of the starting material for synthesis following the milling with the particle size not less than 3 μm to 22% or less in terms of the volumetric integration frequency.

[0021] Since the particle size distribution of the milled starting materials for synthesis is defined as described above, the surface area of the starting materials for synthesis at the time of sintering is sufficient to develop sufficient surface activity. Thus, if the mixture is sintered at a temperature not higher than the melting point of the starting materials for synthesis, single-phase synthesis of the LiFePO₄ carbon composite material may occur satisfactorily. It is noted that milling denotes comminuting and mixing simultaneously.

[0022] In another aspect, the present invention provides a method for the preparation of a non-aqueous electrolyte cell including a cathode having a cathode active material, an anode having an anode active material and a non-aqueous electrolyte, wherein

[0023] in preparing said cathode active material, a starting material for synthesis of a compound represented by the general formula Li_(x)FePO₄, where 0<x≦1, is sintered, mixed, milled and a carbon material is added to the resulting mass at an optional time point in the course of said mixing, milling and sintering;

[0024] Li₃PO₄, Fe₃(PO₄)₂ or hydrates Fe₃(PO₄)₂.nH₂O thereof, where n denotes the number of hydrates, are used as the starting material for synthesis of said Li_(x)FePO₄; and

[0025] the particle size distribution of particles of the starting materials for synthesis following the milling with the particle size not less than 3 μm is set to 22% or less in terms of the volumetric integration frequency.

[0026] Since the particle size distribution of the milled starting material for synthesis is defined as described above, the surface area of the starting material for synthesis at the time of sintering is sufficient to develop sufficient surface activity. Thus, if the mixture is sintered at a temperature not higher than the melting point of the starting materials for synthesis, single-phase synthesis of the LiFePO₄ carbon composite material may occur satisfactorily. By employing this composite material as a cathode active material, a non-aqueous electrolyte cell having superior cell characteristics may be produced.

BRIEF DESCRIPTION OF THE DRAWINGS

[0027]FIG. 1 is a longitudinal cross-sectional view showing an illustrative structure of a non-aqueous electrolyte cell embodying the present invention.

[0028]FIG. 2 is a graph showing Raman spectral peaks of a carbon material.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] Referring to the drawings, preferred embodiments of the present invention will be explained in detail.

[0030] Referring to FIG. 1, a non-aqueous electrolyte cell 1, prepared in accordance with the present invention, includes an anode 2, an anode can 3, holding the anode 2, a cathode 4, a cathode can 5 holding the cathode 4, a separator 6 interposed between the cathode 4 and the anode 2, and an insulating gasket 7. In the anode can 3 and in the cathode can 5 is charged a non-aqueous electrolytic solution.

[0031] The anode 2 is formed by e.g., a foil of metal lithium as an anode active material. If a material capable of doping/undoping lithium is used as the anode active material, the anode 2 is a layer of an anode active material formed on an anode current collector, which may, for example, be a nickel foil.

[0032] As the anode active material, capable of doping/undoping lithium, metal lithium, lithium alloys, lithium-doped electrically conductive high molecular materials or layered compounds, such as carbon materials or metal oxides.

[0033] The binder contained in the anode active material may be any suitable known resin material, routinely used as the binder of the layer of the anode active material for this sort of the non-aqueous electrolyte cell.

[0034] The anode can 3 holds the anode 2, while operating as an external anode of the non-aqueous electrolyte cell 1.

[0035] The cathode 4 is a layer of the cathode active material formed on a cathode current collector, such as an aluminum foil. The cathode active material, contained in the cathode 4, is able to reversibly emit or occlude lithium electro-chemically.

[0036] As the cathode active material, a composite material of carbon and a compound of an olivinic structure represented by the general formula Li_(x)FePO₄, where 0 <x≦1.0, that is the LiFePO₄ carbon composite material, the detailed manufacturing method for which will be explained subsequently, is used.

[0037] In the following explanation, it is assumed that LiFePO₄ is used as Li_(x)FePO₄ and a composite material composed of this compound and carbon is used as the cathode active material.

[0038] The LiFePO₄ carbon composite material is such a material composed of LiFePO₄ particles on the surfaces of which are attached numerous particles of the carbon material having the particle size appreciably smaller than the particle size of the LiFePO₄ particles. Since the carbon material is electrically conductive, the LiFePO₄ carbon composite material, composed of the carbon material and LiFePO₄, is higher in electronic conductivity than e.g., LiFePO₄. That is, since the LiFePO₄ carbon composite material is improved in electronic conductivity due to the carbon particles attached to the LiFePO₄ particles, the capacity proper to LiFePO₄ can be sufficiently manifested. Thus, by using the LiFePO₄ carbon composite material as the cathode active material, the non-aqueous electrolyte secondary cell 1 having a high capacity can be achieved.

[0039] The carbon content per unit weight in the LiFePO₄ carbon composite material is desirably not less than 3 wt %. If the carbon content per unit weight of the LiFePO₄ carbon composite material is less than 3 wt %, the amount of carbon particles attached to LiFePO₄ may be insufficient so that sufficient favorable effect in improving the electronic conductivity may not be realized.

[0040] As the carbon material forming the LiFePO₄ carbon composite material, such a material is preferably used which has an intensity area ratio of diffracted beams appearing at the number of waves of 1570 to 1590 cm⁻¹ to the diffracted beams appearing at the number of waves of 1340 to 1360 cm⁻¹ in the Raman spectrum of graphite in the Raman spectroscopy, or the ratio A(D/G), equal to 0.3 or higher.

[0041] The intensity area ratio A(D/G) is defined as being a background-free Raman spectral intensity area ratio A(D/G) of a G-peak appearing at the number of waves of 1570 to 1590 cm⁻¹ and a D-peak appearing at the number of waves of 1340 to 1360 cm⁻¹ as measured by the Raman spectroscopic method as shown in FIG. 2. The expression “background-free” denotes the state free from noisy portions.

[0042] Among the numerous peaks of the Raman spectrum of Gr, two peaks, namely a peak termed a G-peak appearing at the number of waves of 1570 to 1590 cm⁻¹ and a peak termed a D-peak appearing at the number of waves of 1340 to 1360 cm⁻¹, as discussed above, may be observed. Of these, the D-peak is not a peak inherent in the G-peak, but is a Raman inactive peak appearing when the structure is distorted and lowered in symmetry. So, the D-peak is a measure of a distorted structure of Gr. It is known that the intensity area ratio A(D/G) of the D- and G-peaks is proportionate to a reciprocal of the crystallite size La along the axis a of Gr.

[0043] As such carbon material, an amorphous carbon material, such as acetylene black, is preferably employed.

[0044] The carbon material having the intensity area ratio A(D/G) not less than 0.3 may be obtained by processing such as comminuting with a pulverizing device. A carbon material having an arbitrary ratio A(D/G) may be realized by controlling the pulverizing time duration.

[0045] For example, graphite, as a crystalline carbon material, may readily be destroyed in its structure by a powerful pulverizing device, such as a planetary ball mill, and thereby progressively amorphized, so that the intensity area ratio A(D/G) is concomitantly increased. That is, by controlling the driving time duration of a pulverizing device, such a carbon material having a desired A(D/G) value not less than 0.3 may readily be produced. Thus, subject to pulverization, a crystalline carbon material may also be preferably employed as a carbon material.

[0046] The powder density of the LiFePO₄ carbon composite material is preferably not less than 2.2 gg/cm³. If the material for synthesis of the LiFePO₄ carbon composite material is milled to such an extent that the powder density is not less than 2.2 g/cm³, the resulting LiFePO₄ carbon composite material is comminuted sufficiently to realize a non-aqueous electrolyte secondary cell 1 having a higher charging ratio of the cathode active material and a high capacity. Moreover, since the LiFePO₄ carbon composite material is comminuted to satisfy the aforementioned powder density, its specific surface may be said to be increased. That is, a sufficient contact area may be maintained between LiFePO₄ and the carbon material to improve the electronic conductivity.

[0047] If the powder density of the LiFePO₄ carbon composite material is less than 2.2 g/cm³, the LiFePO₄ carbon composite material is not compressed sufficiently, so that there is a risk that the packing ratio of the active material cannot be improved at the cathode 4.

[0048] On the other hand, the Bulnauer Emmet Teller (BET) specific surface area in the LiFePO₄ carbon composite material is preferably not less than 10.3 m²/g. If the BET specific surface area of the LiFePO₄ carbon composite material is not less than 10.3 m²/g, the surface area of LiFePO₄ per unit weight can be sufficiently increased to increase the contact area between LiFePO₄ and the carbon material to improve the electronic conductivity of the cathode active material.

[0049] The primary particle size of the LiFePO₄ carbon composite material is preferably not larger than 3.1 μm. By the primary particle size of the LiFePO₄ carbon composite material being not larger than 3.1 μm, the surface area of LiFePO₄ per unit area may be sufficiently increased to increase the contact area between LiFePO₄ and the carbon material to improve the electronic conductivity of the cathode active material.

[0050] The binder contained in the layer of the cathode active material may be formed of any suitable known resin material routinely used as the binder for the layer of the cathode active material for this sort of the non-aqueous electrolyte cell.

[0051] The cathode can 5 holds the cathode 4 while operating as an external cathode of the non-aqueous electrolyte cell 1.

[0052] The separator 6, used for separating the cathode 4 and the anode 2 from each other, may be formed of any suitable known resin material routinely used as a separator for this sort of the non-aqueous electrolyte cell. For example, a film of a high molecular material, such as polypropylene, is used. From the relation between the lithium ion conductivity and the energy density, the separator thickness which is as thin as possible is desirable. Specifically, the separator thickness desirably is 50 μm or less.

[0053] The insulating gasket 7 is built in and unified to the anode can 3. The role of this insulating gasket 7 is to prevent leakage of the non-aqueous electrolyte solution charged into the anode can 3 and into the cathode can 5.

[0054] As the non-aqueous electrolyte solution, such a solution obtained on dissolving an electrolyte in a non-protonic aqueous solvent is used.

[0055] As the non-aqueous solvent, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, γ-butyrolactone, sulforane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 2-methyl tetrahydrofuran, 3-methyl-1,3-dioxolane, methyl propionate, methyl lactate, dimethyl carbonate, diethyl carbonate and dipropyl carbonate, for example, may be used. In view of voltage stability, cyclic carbonates, such as propylene carbonate, ethylene carbonate, butylene carbonate or vinylene carbonate, and chained carbonates, such as dimethyl carbonate, diethyl carbonate and dipropyl carbonate, are preferably used. These non-aqueous solvents may be used alone or in combination.

[0056] As the electrolytes dissolved in the non-aqueous solvent, lithium salts, such as LiPF₆, LiClO₄, LiAsF₆, LiBF₄, LiCF₃SO₃ or LiN(CF₃SO₂)₂, may be used. Of these lithium salts, LiPF₆ and LiBF₄ are preferred.

[0057] Although the non-aqueous electrolyte cell, explained above, is the non-aqueous electrolyte secondary cell 1 employing a non-aqueous electrolyte solution, the present invention is not limited thereto, but may be applied to such a cell employing a solid electrolyte as the non-aqueous electrolyte. The solid electrolyte used may be an inorganic solid electrolyte or a high molecular solid electrolyte, such as gel electrolyte, provided that the material used exhibits lithium ion conductivity. The inorganic solid electrolyte may be enumerated by lithium nitride and lithium iodide. The high molecular solid electrolyte is comprised of an electrolyte salt and a high molecular compound dissolving it. The high molecular compound may be an etheric high molecular material, such as poly(ethylene oxide), cross-linked or not, a poly(methacrylate) ester based compound, or an acrylate-based high molecular material, either alone or in combination in the state of being copolymerized or mixed in the molecules. In this case, the matrix of the gel electrolyte may be a variety of high molecular materials capable of absorbing and gelating the non-aqueous electrolyte solution. As these high molecular materials, fluorine-based high molecular materials, such as, for example, poly(vinylidene fluoride) or poly(vinylidene fluoride-CO-hexafluoropropylene), etheric high molecular materials, such as polyethylene oxide, cross-linked or not, or poly(acrylonitrile), may be used. Of these, the fluorine-based high molecular materials are particularly desirable in view of redox stability.

[0058] The method for the preparation of the non-aqueous electrolyte cell 1, constructed as described above, is hereinafter explained.

[0059] First, a composite material of Li_(x)FePO₄ and the carbon material, as a cathode active material, is synthesized by a manufacturing method as now explained.

[0060] For synthesizing the cathode active material, Li_(x)FePO₄ as a starting material for synthesis is kneaded together, milled and sintered. At an optional time point in the course of the mixing, milling and sintering, a carbon material is added to the kneaded starting materials for synthesis. As the Li_(x)FePO₄ starting materials for synthesis, Li₃PO₄, Li₃(PO₄)₂ or a hydrate Fe₃(PO₄)₂ .nH₂O thereof where n denotes the number of hydrates, are used.

[0061] In the following, such a case is explained in which lithium phosphate Li₃PO₄ and a hydrate Fe₃(PO₄)₂.8H₂O thereof, synthesized as explained below, are used as starting materials for synthesis, and in which, after adding a carbon material to these starting materials for synthesis, a number of process steps are executed to synthesize the LiFePO₄ carbon composite material.

[0062] First, the LiFePO₄ starting materials for synthesis and the carbon material are mixed together to form a mixture by way of a mixing step. The mixture from the mixing step is then milled by a milling process, and the milled mixture then is fired by way of a sintering process.

[0063] In the mixing process, lithium phosphate and iron phosphate I octahydrate are mixed together at a pre-set ratio and further added to with a carbon material to form a mixture.

[0064] This iron phosphate I octahydrate, used as a starting material for synthesis, is synthesized by adding disodium hydrogen phosphate duodecahydrate (2Na₂HPO₄.12H₂O) to an aqueous solution obtained on dissolving iron phosphate heptahydrate (FeSO₄.7H₂O) in water and by allowing the resulting mass to dwell for a pre-set time. The reaction of synthesis of iron phosphate I octahydrate may be represented by the following chemical formula (1):

3FeSO₄.7H₂O+2Na2HPO4.12H₂O→Fe₃(PO₄)₂.8H₂O+2Na₂SO₄+37H₂O   (1).

[0065] In iron phosphate I octahydrate, as the material for synthesis, there is contained a certain amount of Fe³⁺ from the synthesis process. If Fe³⁺ is left in the material for synthesis, a trivalent Fe compound is generated by sintering to obstruct single-phase synthesis of the LiFePO₄ carbon composite material. It is therefore necessary to add a reducing agent to the starting materials for synthesis prior to sintering and to reduce Fe³⁺ contained in the starting materials for synthesis at the time of firing to Fe²⁺.

[0066] However, there is a limitation to the capability of the reducing agent in reducing Fe³⁺ to Fe²⁺ by the reducing agent, such that, if the content of Fe³⁺ in the starting materials for synthesis is excessive, it may be an occurrence that Fe³⁺ is not reduced in its entirety but is left in the LiFePO₄ carbon composite material.

[0067] It is therefore desirable that the content of Fe³⁺ in the total iron in the iron phosphate I octahydrate be set to 61 wt % or less. By limiting the content of Fe³⁺ in the total iron in the iron phosphate I octahydrate to 61 wt % or less from the outset, single-phase synthesis of the LiFePO₄ carbon composite material can be satisfactorily achieved without allowing Fe³⁺ to be left at the time of firing, that is without generating impurities ascribable to Fe³⁺.

[0068] It should be noted that, the longer the dwell time in generating iron phosphate I octahydrate, the larger becomes the content of Fe³⁺ in the generated product, so that, by controlling the dwell time so as to be equal to a preset time, iron phosphate I octahydrate having an optional Fe³⁺ can be produced. The content of Fe³⁺ in the total iron in the iron phosphate I octahydrate can be measured by the Mesbauer method.

[0069] The carbon material added to the starting materials for synthesis acts as a reducing agent for reducing Fe³⁺ to Fe²⁺, at the time of sintering, even if Fe²⁺ contained in iron phosphate I octahydrate as the starting materials for synthesis is oxidized to Fe³⁺ by oxygen in atmosphere or due to sintering. Therefore, even if Fe³⁺ is left in the starting materials for synthesis, impurities may be prevented from being generated to assure single-phase synthesis of the LiFePO₄ carbon composite material. Moreover, the carbon material acts as an antioxidant for preventing oxidation of Fe²⁺ contained in the starting materials for synthesis to Fe³⁺. That is, the carbon material prevents oxidation to Fe³⁺ of Fe²⁺ by oxygen present in atmosphere and in a firing oven prior to or during sintering.

[0070] That is, the carbon material acts not only as an electrification agent for improving the electronic conductivity of the cathode active material but also as a reducing agent and as an antioxidant. Meanwhile, since this carbon material is a component of the LiFePO₄ carbon composite material, there is no necessity of removing the carbon material following synthesis of the LiFePO₄ carbon composite material. The result is the improved efficiency in the preparation of the LiFePO₄ carbon composite material.

[0071] It is noted that the carbon content per unit weight of the LiFePO₄ carbon composite material be not less than 3 wt %. By setting the carbon content per unit weight of the LiFePO₄ carbon composite material to not less than 3 wt %, it is possible to utilize the capacity and cyclic characteristics inherent in LiFePO₄ to its fullest extent.

[0072] In the milling process, the mixture resulting from the mixing process is subjected to milling in which pulverization and mixing occur simultaneously. By the milling herein is meant the powerful comminuting and mixing by a ball mill. As the ball mill, a planetary ball mill, a shaker ball mill or a mechano-fusion may selectively be employed.

[0073] By milling the mixture from the mixing process, the starting materials for synthesis and the carbon material can be mixed homogeneously. Moreover, if the starting materials for synthesis is comminuted by milling, the specific surface area of the starting materials for synthesis can be increased, thereby increasing the contact points of the starting materials for synthesis to accelerate the synthesis reaction in the subsequent sintering process.

[0074] According to the present invention, by milling the mixture containing the starting materials for synthesis, the particle size distribution of the particle size not less than 3 μm it set to not larger than 22% in terms of the volumetric integration frequency. Since the particle size distribution of the starting materials for synthesis is prescribed in the above range, the starting materials for synthesis has a surface area sufficient to produce surface activity for carrying out the synthesis reaction. Thus, even if the sintering temperature is of a low value of e.g., 600° C. which is lower than the melting point of the starting materials for synthesis, the reaction efficiency is optimum, thus realizing the single-phase synthesis of the LiFePO₄ carbon composite material satisfactorily.

[0075] Moreover, the milling is desirably executed so that the powder density of the LiFePO₄ carbon composite material will be 2.2 g/cm³ or higher. By comminuting the starting materials for synthesis to give the above defined powder density, the specific surface area of LiFePO₄ and hence the contact area between LiFePO₄ and the carbon material can be increased to improve the electronic conductivity of the cathode active material.

[0076] Thus, by milling the mixture containing the starting materials for synthesis, the cathode active material which can achieve the non-aqueous electrolyte secondary cell 1 having a high capacity is manufactured.

[0077] In the firing process, the milled mixture from the milling process is sintered. By sintering the mixture, lithium phosphate can be reacted with iron phosphate I octahydrate to synthesize LiFePO₄. The synthesis reaction of LiFePO₄ may be represented by the following reaction formula (2):

Li₃PO₄+Fe₃(PO₄)₂ .nH₂O→3LiFePO₄ +nH₂O   (2)

[0078] where n denotes the number of hydrates and is equal to 0 for an anhydride. In the chemical formula (2), Li₃PO₄ is reacted with Fe₃(PO₄)₂ or its hydrate Fe₃(PO₄)₂ .nH₂O where n denotes the number of hydrates.

[0079] As may be seen from the chemical formula (2), no by-product is yielded if Fe₃(PO₄)₂ is used as a starting materials for synthesis. On the other hand, if Fe₃(PO₄)₂ .nH₂O is used, water, which is non-toxic, is by-produced.

[0080] Heretofore, lithium carbonate, ammonium dihydrogen phosphate and iron acetate II, as syntheses materials, are mixed at a pre-set ratio and sintered to synthesize LiFePO₄ by the reaction shown by the chemical formula (3):

Li₂CO₃+2Fe(CH₃COO)₂+2NH₄H₂PO₄ →2LiFePO₄+CO₂+H₂+2NH₃+4CH₃COOH   (3).

[0081] As may be seen from the reaction formula (3), toxic by-products, such as ammonia or acetic acid, are generated on sintering with the conventional synthesis method for LiFePO₄. So, a large-scale equipment, such as gas collector, is required for processing these toxic by-products, thus raising the cost. In addition, the yield of LiFePO₄ is lowered because these by-products are generated in large quantities.

[0082] According to the present invention, in which Li₃PO₄, Fe₃(PO₄)₂ or its hydrate Fe₃(PO₄)₂ .nH₂O, where n denotes the number of hydrates, is used as the starting material for synthesis, targeted LiFePO₄ can be produced without generating toxic by-products. In other words, safety in sintering may be appreciably improved as compared to the conventional manufacturing method. Moreover, while a large-scale processing equipment is heretofore required for processing toxic by-products, the manufacturing method of the present invention yields only water, which is innoxious, as a by-product, thus appreciably simplifying the processing step to allow to reduce size of the processing equipment. The result is that the production cost can be appreciably lower than if ammonia etc which is by-produced in the conventional system has to be processed. Moreover, since the by-product is yielded only in minor quantities, the yield of LiFePO₄ may be improved significantly.

[0083] Although the sintering temperature in sintering the mixture may be 400 to 900° C. by the above synthesis method, it is preferably 600° C. or thereabouts in consideration of the cell performance. If the sintering temperature is less than 400° C., neither the chemical reaction not crystallization proceeds sufficiently such that there is the risk that the phase of impurities such as Li₃PO₄ of the starting materials for synthesis may persist and hence the homogeneous LiFePO₄ cannot be produced. If conversely the sintering temperature exceeds 900° C., crystallization proceeds excessively so that the LiFePO₄ particles are coarse in size to decrease the contact area between LiFePO₄ and the carbon material to render it impossible to achieve sufficient discharging capacity.

[0084] During sintering, Fe in the LiFePO₄ carbon composite material synthesized is in the bivalent state. So, in the temperature of the order of 600° C. as the synthesis temperature, Fe in the LiFePO₄ carbon composite material is promptly oxidized to Fe³⁺by oxygen in the sintering atmosphere in accordance with the chemical formula shown by the chemical formula (4):

6FiFePO₄+3/2O₂→2Li₃Fe₂(PO₄)₃+Fe₂O₃   (4)

[0085] so that impurities such as trivalent Fe compounds are produced to obstruct the single-phase synthesis of the LiFePO₄ carbon composite material.

[0086] So, inert gases, such as nitrogen or argon, or reducing gases, such as hydrogen or carbon monoxide, are used as the sintering atmosphere, while the oxygen concentration in the sintering atmosphere is desirably set to a range within which Fe in the LiFePO₄ carbon composite material is not oxidized, that is to not larger than 1012 ppm in volume. By setting the oxygen concentration in the sintering atmosphere to 1012 ppm in volume or less, it is possible to prevent Fe from being oxidized even at the synthesis temperature of 600° C. or thereabouts to achieve the single-phase synthesis of the LiFePO₄ carbon composite material.

[0087] If the oxygen concentration in the sintering atmosphere is 1012 ppm in volume or higher, the amount of oxygen in the sintering atmosphere is excessive, such that Fe in the LiFePO₄ carbon composite material is oxidized to Fe³⁺ to generate impurities to obstruct the single-phase synthesis of the LiFePO₄ carbon composite material.

[0088] As for takeout of the sintered LiFePO₄ carbon composite material, the takeout temperature of the sintered LiFePO₄ carbon composite material, that is th temperature of the LiFePO₄ carbon composite material when exposed to atmosphere, is desirably 305° C. or lower. On the other hand, the takeout temperature of the sintered LiFePO₄ carbon composite material is more desirably 204° C. or lower. By setting the takeout temperature of the LiFePO₄ carbon composite material to 305° C. or lower, Fe in the sintered LiFePO₄ carbon composite material is oxidized by oxygen in atmosphere to prevent impurities from being produced.

[0089] If the sintered LiFePO₄ carbon composite material is taken out in an insufficiently cooled state, Fe in the LiFePO₄ carbon composite material is oxidized by oxygen in atmosphere, such that impurities tend to be produced. However, if the LiFePO₄ carbon composite material is cooled to too low a temperature, the operating efficiency tends to be lowered.

[0090] Thus, by setting the takeout temperature of the sintered LiFePO₄ carbon composite material to 305° C. or lower, it is possible to prevent Fe in the sintered LiFePO₄ carbon composite material from being oxidized by oxygen in atmosphere and hence to prevent impurities from being generated to maintain the operation efficiency as well as to synthesize the LiFePO₄ carbon composite material having desirable characteristics as the cell with high efficiency.

[0091] Meanwhile, the cooling of the as-sintered LiFePO₄ carbon composite material is effected in a sintering furnace. The cooling method used may be spontaneous cooling or by forced cooling. However, if a shorter cooling time, that is a higher operating efficiency, is envisaged, forced cooling is desirable. In case the forced cooling is used, it is sufficient if a gas mixture of oxygen and inert gases, or only the inert gases, are supplied into the sintering furnace so that the oxygen concentration in the sintering furnace will be not higher than the aforementioned oxygen concentration, that is 1012 ppm in volume or less.

[0092] Although the carbon material is added prior to milling, it may be added after milling or after sintering.

[0093] However, if the carbon material is added after sintering, the reducing effect in sintering or the effect in prohibiting oxidation cannot be realized but the carbon material is used only for improving the electrical conductivity. Therefore, in case the carbon material is added after the sintering, it is necessary to prevent Fe³⁺ from being left by other means.

[0094] In the carbon material is added after sintering, the product synthesized by sintering is not the LiFePO₄ carbon composite material but is LiFePO₄. So, after adding the carbon material, synthesized by sintering, milling is again carried out. By again carrying out the milling, the carbon material added is comminuted and more liable to be attached to the surface of LiFePO₄. By the second milling, LiFePO₄ and the carbon material is mixed together sufficiently so that the comminuted carbon material can be homogeneously attached to the surface of LiFePO₄. Thus, even when the carbon material is added after the sintering, it is possible to obtain a product similar to one obtained in case the addition of the carbon material is effected prior to milling, that is the LiFePO₄ carbon composite material. On the other hand, the meritorious effect similar to that described above can be realized.

[0095] The non-aqueous electrolyte secondary cell 1, employing the LiFePO₄ carbon composite material, obtained as described above, as the cathode active material, may, for example, be prepared as follows:

[0096] As the anode 2, the anode active material and the binder are dispersed in a solvent to prepare a slurried anode mixture. The so-produced anode mixture is evenly coated on a current collector and dried in situ to form a layer of the anode active material to produce the anode 2. As the binder of the anode mixture, any suitable known binder may be used. In addition, any desired known additive may be added to the anode mixture. It is also possible to use metal lithium, which becomes the anode active material, directly as the anode 2.

[0097] As the cathode 4, the LiFePO₄ carbon composite material, as the cathode active material, and the binder, are dispersed in a solvent to prepare a slurried cathode mixture. The so-produced cathode mixture is evenly coated on the current collector and dried in situ to form a layer of the cathode active material to complete the cathode 4. As the binder of the cathode active material, any suitable known binder may be used, whilst any desirable known additive may be added to the cathode mixture.

[0098] The non-aqueous electrolyte may be prepared by dissolving an electrolyte salt in a non-aqueous solvent.

[0099] The anode 2 is held in the anode can 3, the cathode is held in the cathode can 5 and the separator 6 formed by a porous polypropylene film is arranged between the anode 2 and the cathode 4. The non-aqueous electrolytic solution is injected into the anode can 3 and into the cathode can 5. The anode can 3 and the cathode can 5 are caulked together and secured with the interposition of the insulating gasket 7 in-between to complete a coin-shaped non-aqueous electrolyte cell 1.

[0100] The non-aqueous electrolyte cell 1, prepared as described above, having the LiFePO₄ carbon composite material as the cathode active material, has a high charging ratio of the cathode active material and is superior in electronic conductivity. Thus, with this non-aqueous electrolyte cell 1, lithium ion doping/undoping occurs satisfactorily so that the cell may be of a larger capacity. In addition, since the superior cyclic characteristics inherent in LiFePO₄ may be manifested sufficiently, the cell may be of a larger capacity and superior in cyclic characteristics.

[0101] There is no particular limitation to the shape of the non-aqueous electrolyte cell 1 of the above-mentioned embodiment, such that the cell may be cylindrically-shaped, square-shaped, coin-shaped or button-shaped, while it may be of a thin type or of a larger format.

EXAMPLES

[0102] The present invention is hereinafter explained based on specified experimental results. Here, in order to check for the meritorious effect of the present invention, a LiFePO₄ carbon composite material was synthesized and, using this LiFePO₄ carbon composite material as a cathode active material, a non-aqueous electrolyte cell was prepared, and its characteristics were evaluated.

Example 1

[0103] An LiFePO₄ carbon composite material was synthesized as a cathode active material by the following method.

[0104] First, Li₃PO₄ and Fe₃(PO₄)₂.8H₂O were mixed to give an elementary ratio of lithium to iron equal to 1:1. To the resulting mixture were added acetylene black powders, as the amorphous carbon material, so that the acetylene black powders accounted for 10 wt % of the sintered product in its entirety. The mixture and alumina balls, each 10 mm in diameter, were charged into an alumina pot 100 mm in diameter, with the weight ratio of the mixture to the alumina balls equal to 1:2. The mixture was milled using a planetary ball mill. As this planetary ball mill, a planetary rotating pot mill for test, manufactured by ITO SEISAKUSHO KK under the trade name of LA-PO4, was used, and the mixture was milled under the following conditions:

[0105] Conditions for planetary ball milling

[0106] radius of rotation about sun gear: 200 mm

[0107] number of revolutions about the sun gear: 250 rpm

[0108] number of revolutions about a planetary gear itself: 250 rpm

[0109] driving time duration: 900 minutes.

[0110] Next, the particle size distribution of the mixture, milled as described above, was measured as follows: First, the milled mixture and a solvent composed of methylethylketone, toluene and cyclohexanone were charged into a cell (screw tube vial). The sample in the cell was dispersed ultrasonically and, using a unit HRA manufactured by MICROTRA Inc., the particle size distribution of the mixture was measured. The particle size distribution, indicated by the particles having the particle size not less than 3 μm, was found in terms of a volumetric integration frequency.

[0111] The mixture from the particle size distribution measurement step was charged into a ceramic crucible and fired for five hours at 600° C. in an electrical oven kept in a nitrogen atmosphere to produce an LiFePO₄ carbon composite material.

Example 2

[0112] An LiFePO₄ carbon composite material was prepared in the same way as in Example 1 except setting the milling time, that is the driving time of the planetary type ball mill, to 300 minutes.

Example 3

[0113] An LiFePO₄ carbon composite material was prepared in the same way as in Example 1 except setting the milling time, that is the driving time of the planetary type ball mill, to 180 minutes.

Example 4

[0114] An LiFePO₄ carbon composite material was prepared in the same way as in Example 1 except setting the milling time, that is the driving time of the planetary type ball mill, to 120 minutes.

Example 5

[0115] An LiFePO₄ carbon composite material was prepared in the same way as in Example 1 except setting the milling time, that is the driving time of the planetary type ball mill, to 60 minutes.

Example 6

[0116] An LiFePO₄ carbon composite material was prepared in the same way as in Example 1 except setting the milling time, that is the driving time of the planetary type ball mill, to 45 minutes.

Example 7

[0117] An LiFePO₄ carbon composite material was prepared in the same way as in Example 1 except setting the milling time, that is the driving time of the planetary type ball mill, to 30 minutes.

Comparative Example 1

[0118] An LiFePO₄ carbon composite material was prepared in the same way as in Example 1 except setting the milling time, that is the driving time of the planetary type ball mill, to 20 minutes.

Comparative Example 2

[0119] An LiFePO₄ carbon composite material was prepared in the same way as in Example 1 except setting the milling time, that is the driving time of the planetary type ball mill, to 10 minutes.

Comparative Example 3

[0120] An LiFePO₄ carbon composite material was prepared in the same way as in Example 1 except setting the milling time, that is the driving time of the planetary type ball mill, to 5 minutes.

[0121] X-ray diffractometry was carried out on the products obtained as described above. The results are shown in Table 1 along with the particle size distribution indicated by the particles having the particle size diameter not less than 3 μm in terms of the volumetric integration frequency. This particle size distribution is indicated as volumetric particle size distribution in Table 1. In this Table 1, the sample products matched to the powder X-ray diffraction lines stated in JCPDS-No. 401499 and in which no diffraction lines were observed are marked ◯as those sample in which single-phase synthesis of the LiFePO₄ carbon composite material has occurred, whereas those sample products not matched to the powder X-ray diffraction lines stated in JCPDS-No. 401499 or those sample products matched to the powder X-ray diffraction lines stated in JCPDS-No.401499 but in which other diffraction lines were observed, are marked ×. TABLE 1 volumetric particle size milling distribution (%) time (min) synthesizability Ex.1 0.6 900 ∘ Ex.2 1 300 ∘ Ex.3 3 180 ∘ Ex.4 6 120 ∘ Ex.5 14 60 ∘ Ex.6 17 45 ∘ Ex.7 22 30 ∘ Comp. Ex.1 29 20 x Comp. Ex.2 35 10 x Comp. Ex.3 59 5 x

[0122] It may be seen from Table 1 that the Examples 1 to 7 of the starting materials for synthesis of the LiFePO₄ carbon composite material, in which the particle size distribution of the particle size not less than 3 μm, is not larger than 22% in terms of the volumetric integration frequency, are matched to the powder ray diffraction lines stated in JCPDS-NO.401499, while no other diffraction lines are identified, thus indicating that single-phase synthesis of the LiFePO₄ carbon composite material has been achieved satisfactorily.

[0123] Conversely, the Comparative Examples 1 to 3 in the starting materials for synthesis of the LiFePO₄ carbon composite material, in which the particle size distribution of the particle size not less than 3 μm, is larger than 22% in terms of the volumetric integration frequency, are not matched to the powder ray diffraction lines stated in JCPDS-NO.401499. Even if these Comparative Examples are matched to the powder ray diffraction lines stated in JCPDS-NO.401499, other diffraction are identified. Thus, with these Comparative Examples 1 to 3, it is seen that the single-phase synthesis of the LiFePO₄ carbon composite material has not been achieved.

[0124] It may be seen from above that by setting the particle size distribution of the particles with the particle size not less than 3 μm so as to be 22% or less in terms of the volumetric integration frequency, the surface area of the sample mixture prior to sintering can be increased, so that, even if the sintering temperature is 600° C., single-phase synthesis of the LiFePO₄ carbon composite material has been achieved satisfactorily.

[0125] On the other hand, comparison of Examples 1 to 7 to the Comparative Examples 1 to 3 indicates that the particle size distribution of the starting materials for synthesis depends on the milling time, so that the starting materials for synthesis having the desired particle size can be produced by controlling the milling time.

[0126] A non-aqueous electrolyte cell, employing the LiFePO₄ carbon composite material, produced as described above, was prepared.

Example 8

[0127] 95 parts by weight of the LiFePO₄ carbon composite material, as the cathode active material, prepared in Example 1, and 5 parts by weight of poly (vinylidene fluoride), in the form of fluorine resin powders, as a binder, were mixed together and molded under pressure to form a pellet-shaped cathode having a diameter of 15.5 mm and a thickness of 0.1 mm.

[0128] A foil of metal lithium was then punched to substantially the same shape as the cathode to form an anode.

[0129] Then, a non-aqueous electrolyte solution was prepared by dissolving LiPF₆ in a solvent mixture comprised of equal volumes of propylene carbonate and dimethyl carbonate, at a concentration of 1 mol/l, to prepare a non-aqueous electrolyte solution.

[0130] The cathode, thus prepared, was charged into the cathode can, while the anode was held in the anode can and the separator was arranged between the cathode and the anode. The non-aqueous electrolytic solution was injected into the anode can and into the cathode can. The anode can and the cathode can were caulked and secured together to complete a type 2016 coin-shaped test cell having a diameter of 20 mm and a thickness of 1.6 mm.

Example 9

[0131] A coin-shaped test cell was prepared in the same way as in Example 8 except using the product obtained as in Example 8 as the cathode active material.

Comparative Example 4

[0132] A coin-shaped test cell was prepared in the same way as in Example 8 except using the product obtained as in Comparative Example 1 as the cathode active material.

Comparative Example 5

[0133] A coin-shaped test cell was prepared in the same way as in Example 8 except using the product obtained as in Comparative Examples 2 as the cathode active material.

[0134] On the coin-shaped test cells , prepared as described above, the charging/discharging tests were conducted as now explained to evaluate the initial discharge capacity.

[0135] Test of charging/discharging cyclic characteristics

[0136] Each test cell was charged at a constant current and, at a time point the cell voltage reached 4.2 V, the constant current charging was switched to constant voltage charging and charging was carried out as the cell voltage was kept at 4.2 V. The charging was terminated at a time point the current value fell to 0.01 mA/cm2 or less. Each test was then discharged. The discharging was terminated at a time point the cell voltage fell to 2.0 V.

[0137] With the above process as one cycle, 50 cycles were carried out, and the discharging capacity at the first cycle and that at the fifth cycle were found. The ratio of the discharging capacity at the fiftieth cycle (C2) to the discharging capacity at the first cycle (C1)(C2/C1) ×100 was found as the capacity upkeep ratio. Meanwhile, both the charging and the discharging were carried out at ambient temperature (25° C.), as the current density at this time was set to 0.1 mA/cm2. The results are shown in Table 2. TABLE 2 volumetric particle size distribution (%) initial discharge capacity Ex.8 0.6 160 Ex.9 22 160 Comp. Ex.4 29 87 Comp. Ex.5 35 72

[0138] It may be seen from Table 2 that, in the Examples 8 and 9 employing the cathode active material in which single-phase synthesis of the LiFePO₄ carbon composite material was achieved, the initial discharge capacity is satisfactory, whereas, in the Comparative Examples 4 and 5 in which single-phase synthesis of the LiFePO₄ carbon composite material was not achieved, the initial discharge capacity is decreased appreciably, thus indicating that the LiFePO₄ carbon composite material prepared in these Comparative Examples are not proper as the cathode active material. It may be said that, for producing an LiFePO₄ carbon composite material satisfactory as a cathode active material, the particle size distribution of the particles with the particle size not less than 3 μm in the starting materials for synthesis of the LiFePO₄ carbon composite material needs to be 22% or less in terms of the volumetric integration frequency.

[0139] Next, a polymer cell was prepared to evaluate its characteristics.

Example 10

[0140] A gelated electrode was prepared as follows: First, polyvinylidene fluoride, in which was copolymerized 6.9 wt % of hexafluoropropylene, a non-aqueous electrolyte and dimethyl carbonate, were mixed, agitated and dissolved to a sol-like electrolytic solution. To the sol-like electrolytic solution was added 0.5 wt % of vinylene carbonate VC to form a gelated electrolytic solution. As the non-aqueous electrolyte solution, such a solution obtained on mixing ethylene carbonate EC and propylene carbonate PC at a volumetric ratio of 6:4 and on dissolving LiPF₆ at a rate of 0.85 mol/kg in the resulting mixture was used.

[0141] A cathode was then prepared as follows: First, 95 parts by weight of the LiFePO₄ carbon composite material, prepared in Example 8, and 5 parts by weight of poly (vinylidene fluoride), in the form of fluorine resin powders, as a binder, were mixed together, and added to with N-methyl pyrrolidone to give a slurry, which slurry was coated on an aluminum foil 20 μm in thickness, dried in situ under heating and pressed to form a cathode coating film. A gelated electrolytic solution then was applied to one surface of the cathode coating film and dried in situ to remove the solvent. The resulting product was punched to a circle 15 mm in diameter, depending on the cell diameter, to form a cathode electrode.

[0142] The anode then was prepared as follows: First, 10 wt % of fluorine resin powders, as a binder, were mixed into graphite powders, and added to with N-methyl pyrrolidone to form a slurry, which then was coated on a copper foil, dried in situ under heating and pressed to form an anode coating foil. On one surface of the anode coating foil was applied a gelated electrolytic solution and dried in situ to remove the solvent. The resulting product was punched to a circle 16.5 mm in diameter, depending on the cell diameter, to form an anode electrode.

[0143] The cathode, thus prepared, was charged into the cathode can, while the anode was held in the anode can and the separator was arranged between the cathode and the anode. The anode can and the cathode can were caulked and secured together to complete a type 2016 coin-shaped lithium polymer cell having a diameter of 20 mm and a thickness of 1.6 mm.

[0144] The polymer cell of Example 10, prepared as described above, was put to the aforementioned test on charging/discharging cyclic characteristics to find the initial discharging capacity and capacity upkeep ratio after 30 cycles.

[0145] Test on charging/discharging cyclic characteristics

[0146] The charging/discharging cyclic characteristics were evaluated based on the volume upkeep ratio after repeated charging/discharging.

[0147] Each test cell was charged at a constant current and, at a time point the cell voltage reached 4.2 V, the constant current charging was switched to constant voltage charging and charging was carried out as the cell voltage was kept at 4.2 V. The charging was terminated at a time point the current value fell to 0.01 mA/cm² or less. Each test was then discharged. The discharging was terminated at a time point the cell voltage fell to 2.0 V.

[0148] With the above process as one cycle, 30 cycles were carried out, and the discharging capacity at the first cycle and that at the 30th cycle were found. The ratio of the discharging capacity at the 30th cycle (C2) to the discharging capacity at the first cycle (C1)(C2/C1)×100 was found as the capacity upkeep ratio. Meanwhile, both the charging and the discharging were carried out at ambient temperature (25° C.), as the current density at this time was set to 0.1 mA/cm². The results are also shown in Table 1.

[0149] The results are shown in Table 2. TABLE 3 Volumetric particle initial discharging volumetric upkeep ratio size distribution capacity after 30 cycles Ex.10 22% 158 mAh/g 95.8%

[0150] As may be seen from Table 2, both the initial discharging capacity and capacity upkeep ratio after 30 cycles are of satisfactory values. From this, it may be seen that the cathode active material prepared in accordance with the manufacturing method of the present invention gives meritorious effects, such as improved discharge capacity and improved cyclic characteristics, even in case the gelated electrolyte is used in place of the non-aqueous electrolyte as the non-aqueous electrolytic solution. 

What is claimed is:
 1. A method for the preparation of a cathode active material comprising: mixing, milling and sintering a starting material for synthesis of a compound represented by the general formula Li_(x)FePO₄, where 0<x>1, and adding a carbon material to the resulting mass at an optional time point in the course of said mixing, milling and sintering; employing Li₃PO₄, Fe₃(PO₄)₂ or hydrates Fe₃(PO₄)₂ nH₂O thereof, where n denotes the number of hydrates, as the starting material for synthesis of said Li_(x)FePO₄; and setting the particle size distribution of particles of said starting material for synthesis following the milling with the particle size not less than 3 μm to 22% or less in terms of the volumetric integration frequency.
 2. A method for the preparation of a non-aqueous electrolyte cell including a cathode having a cathode active material, an anode having an anode active material and a non-aqueous electrolyte, comprising: mixing, milling and sintering a starting material for synthesis of a compound represented by the general formula Li_(x)FePO₄, where 0<x>1, in preparing said cathode active material, and adding a carbon material to the resulting mass at an optional time point in the course of said mixing, milling and sintering; employing Li₃PO₄, Fe₃(PO₄)₂ or hydrates Fe₃(PO₄)₂ nH₂O thereof, where n denotes the number of hydrates, as the starting materials for synthesis of said Li_(x)FePO₄; and setting the particle size distribution of particles of the starting material for synthesis following the milling with the particle size not less than 3 μm to 22% or less in terms of the volumetric integration frequency.
 3. The method for the preparation of a non-aqueous electrolyte cell according to claim 2 wherein said non-aqueous electrolyte comprising a non-agueous electrolyte including a dissolved electrolyte in a non-aqueous sdvent.
 4. The method for the preparation of a non-aqueous electrolyte cell according to claim 2 wherein said non-aqueous electrolyte is a solid electrolyte.
 5. The method for the preparation of a non-aqueous electrolyte cell according to claim 2 wherein said anode is a material capable of doping/undoping lithium.
 6. The method for the preparation of a non-aqueous electrolyte cell according to claim 2 wherein said anode is a carbon material. 